Optimization of the MnCeOx system for the catalytic wet oxidation of phenol with oxygen (CWAO)

Abstract

A class of MnCeOx catalysts has been synthesized via the new redox-precipitation route in alternative to the conventional co-precipitation technique. The effects of preparation method, composition and calcination temperature on catalyst texture, dispersion and reduction pattern properties have been addressed. Redox-precipitated systems exhibit high surface area (SA, 120–170m2/g), large pore volume (PV, 0.4–0.5cm3/g) and a “narrow” pore size distribution (PSD) in a wide range of the Mn/Ce ratio (1/3–3/1). A quasi-molecular dispersion markedly improves oxide-support interactions and reducibility of the active phase. Redox-precipitated systems show a superior performance in the catalytic wet oxidation of phenol with oxygen (CWAO) at 373K in terms of substrate and total organic carbon (TOC) elimination and mineralization (i.e., CO2 formation) selectivity. Carbon mass-balance from TG-DSC data of used catalysts and CO2 selectivity values signal that the CWAO of phenol proceeds via a L–H reaction path, the oxidation of C-containing species being the rate limiting step (r.l.s.). Then, an optimum average pore diameter (APD, 10–15nm) enhances the rate of the adsorption step, while a straight relation between CO2 selectivity and reducibility prove that dispersion and redox properties of the active phase control the mineralization activity of the MnCeOx system.